CN111193019B - Lithium supplement additive, preparation method thereof and lithium ion battery - Google Patents
Lithium supplement additive, preparation method thereof and lithium ion battery Download PDFInfo
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- CN111193019B CN111193019B CN202010030913.3A CN202010030913A CN111193019B CN 111193019 B CN111193019 B CN 111193019B CN 202010030913 A CN202010030913 A CN 202010030913A CN 111193019 B CN111193019 B CN 111193019B
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- 229910052744 lithium Inorganic materials 0.000 title abstract description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 76
- 239000013589 supplement Substances 0.000 title abstract description 56
- 239000000654 additive Substances 0.000 title abstract description 46
- 230000000996 additive effect Effects 0.000 title abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000011162 core material Substances 0.000 abstract description 61
- 229910052751 metal Inorganic materials 0.000 abstract description 31
- 239000002184 metal Substances 0.000 abstract description 30
- 238000010438 heat treatment Methods 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910018068 Li 2 O Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011257 shell material Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 6
- 229910001947 lithium oxide Inorganic materials 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- -1 transition metal nitride Chemical class 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910014913 LixSi Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium supplement additive, a preparation method thereof and a lithium ion battery. The lithium supplement additive comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 O and a metal M, the shell comprising SiOx and carbon. The method comprises the following steps: 1) Mixing oxide of metal M with metal lithium, and heating and reacting under protective atmosphere to obtain a core material; 2) Mixing a core material, a pore-forming agent and an organic silicon source in a solvent, adding an alkaline substance, reacting, carrying out solid-liquid separation after the reaction, and sintering the obtained solid in a protective atmosphere to obtain the lithium supplement additive. The lithium supplement additive provided by the invention has high stability and can be completely compatible with the existing lithium battery processing and manufacturing technology.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium supplement additive, a preparation method thereof and a lithium ion battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, li + Intercalation and deintercalation to and from two electrodes: upon charging, li + The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. Lithium ion batteries seek high energy density, and increasing capacity is one of the methods for increasing energy density.
The first coulombic efficiency of the anode and cathode materials of the lithium ion battery is less than 100%, irreversible loss of active lithium ions is caused, for example, the SEI film formed by the cathode consumes the lithium ions, and thus the capacity is reduced.
In the charge and discharge cycle of the lithium ion battery, the capacity of the lithium ion battery is gradually attenuated in the cycle process due to the consumption of lithium ions, so that the lithium ion battery is scrapped. In the charge-discharge cycle of the lithium ion battery, factors consuming lithium ions include: lithium ions are consumed due to the formation of an SEI film, lithium ions are consumed due to side reactions in charge-discharge cycles, active lithium participating in charge-discharge cycles is reduced due to structural collapse of active materials, and the like, and different lithium ion battery systems have different lithium ion loss degrees.
Lithium supplement materials of lithium batteries generally adopt lithium powder/lithium metal and LixSi @ Li 2 O, lithiated transition metal nitride, li 5 FeO 4 、Li 6 CoO 4 、Li 2 NiO 2 、Metal/Li 2 O, and the like. The introduction of these lithium supplement materials may have negative effects such as increase of electrical core impedance, oxygen evolution, metal dissolution, etc., and the suitability of the lithium supplement materials to the existing electrical core system and processing technology still needs to be improved, such as the processing performance and stability of the materials.
CN109786746A discloses a positive plate, a lithium ion battery positive electrode lithium supplement material and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a positive electrode lithium supplement material matrix; mixing the anode lithium supplement material matrix and a carbon source by using ethanol as a solvent to obtain a mixed solution; and volatilizing the solvent from the mixed solution, and calcining in an inert atmosphere to obtain the lithium-supplement material with the carbon-coated surface for the lithium ion battery anode.
CN105098188A provides an additive for a lithium ion battery positive electrode material, a preparation method thereof, a positive electrode material containing the additive and a lithium ion battery, wherein the additive has a core-shell structure, the core material comprises inorganic lithium salt modified by a silane coupling agent, the shell material comprises a low-melting-point polymer, and the porosity of the shell is 0.01% -20%.
CN107819113A provides a lithium supplement additive, a preparation method and an application thereof. The core material is conductive carbon material, the shell material is lithium oxide, the lithium oxide is deposited on the surface of the conductive carbon material, and nano-layer shells are formed by nano-sized lithium oxide particles. According to the lithium supplement additive, the lithium oxide and the conductive carbon material are compounded, the lithium oxide is used for supplementing lithium, and the conductive carbon material is used for dredging electrons, so that the utilization rate of the lithium oxide is improved, and the lithium can be supplemented to the anode or the cathode.
CN109873129A provides a composite positive active material, a preparation method thereof, a positive electrode and a battery. The composite anode active material has a core-shell structure, wherein the core contains the anode active material, the shell layer contains a silicate material with a pmn crystal form structure, the silicate material contains Li and M elements, and the M elements are metal elements with a divalent valence state. The composite anode active material provided by the scheme has a core-shell structure, the lithium supplement agent is distributed on a shell layer of the composite anode active material with the core-shell structure, and the anode active material is formed in the core.
However, the above solutions all have the problems that the stability of the lithium supplement material needs to be improved, and the lithium supplement material is not easily compatible with the existing lithium ion battery processing and manufacturing technology.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a lithium supplement additive, a preparation method thereof and a lithium ion battery. The lithium supplement additive provided by the invention has high stability and can be completely compatible with the existing lithium battery processing and manufacturing technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium supplement additive, which comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 O and a metal M, the shell comprising SiOx and carbon.
In the lithium supplement additive provided by the invention, the core material has a lithium supplement function, but the conductivity is poor, and metal elution possibly occurs at a high potential to influence the performance of a battery cell.
The lithium supplement additive provided by the invention is suitable for supplementing lithium for the anode.
In the lithium supplement additive provided by the invention, li in the inner core 2 O and the metal M are mixed together to form a mixture, and SiOx and carbon in the envelope are also mixed together to form a mixture.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the metal M includes any one or a combination of at least two of Mn, fe, co, ni, and Cu.
Preferably, in the lithium supplement additive, li 2 The molar ratio of the lithium element in O to the M element in the metal M is 1:1-4:1, for example 1:1, 2:1, 3:1 or 4:1. In the present invention, if the lithium in the core is too much and the M element is too little, li will be caused 2 The irreversible discharge capacity is reduced due to excessive O; if the lithium in the core is too small, the M element is too much, resulting in a decrease in the irreversible discharge capacity.
In the SiOx, x is 0 to 2 and does not include 0, for example, 1, 1.5, or 2.
Preferably, in the lithium supplement additive, the thickness of the shell is 1-50nm, such as 1nm, 5nm, 10nm, 20nm, 30nm, 40nm or 50nm.
Preferably, in the lithium supplement additive, the shell has a porous structure. The porous structure can better promote the permeability of lithium element and better ensure the lithium supplementing effect.
In a second aspect, the present invention provides a method for preparing the lithium supplement additive according to the first aspect, the method comprising the steps of:
(1) Mixing oxide of metal M with metal lithium, and heating and reacting under protective atmosphere to obtain a core material;
(2) Mixing the core material and the organic silicon source in the step (1) in a solvent, adding an alkaline substance, reacting, carrying out solid-liquid separation after the reaction, and sintering the obtained solid in a protective atmosphere to obtain the lithium supplement additive.
The preparation method provided by the invention replaces metal M with metal lithium in step (1) to obtain metal M and Li 2 O, the reaction equation of which is: m x O y +2yLi–>yLi 2 O+xM。
According to the preparation method provided by the invention, in the step (2), the silicon coating layer is prepared on the surface of the core material by using the organic silicon source, and a certain amount of carbon can be formed after the pore-forming agent is sintered, so that the conductivity of the material can be improved.
In a preferred embodiment of the present invention, the molar ratio of the metal lithium in the step (1) to the metal M in the oxide of the metal M is 1:1-4:1, for example, 1:1, 2:1, 3:1, or 4:1.
Preferably, the protective atmosphere of step (1) comprises a nitrogen atmosphere and/or an argon atmosphere.
Preferably, the average particle size of the metal M oxide in step (1) is 200nm to 50 μ M, such as 200nm, 500nm, 1 μ M, 5 μ M, 10 μ M, 20 μ M, 30 μ M, 40 μ M, or 50 μ M, and the like.
As a preferable technical scheme of the invention, the heating reaction in the step (1) is two-stage heating.
Preferably, in the two-stage heating, the temperature of the first stage heating is 180-190 ℃, such as 180 ℃, 182 ℃, 184 ℃, 186 ℃, 188 ℃ or 190 ℃.
Preferably, in the two-stage heating, the first stage heating time is 20-40min, such as 20min, 25min, 30min, 35min or 40min.
Preferably, in the two-stage heating, the temperature of the second stage heating is 195-205 ℃, such as 195 ℃, 197 ℃, 200 ℃, 203 ℃ or 205 ℃ and the like.
Preferably, in the two-stage heating, the second stage heating time is 2.5-3.5h, such as 2.5h, 2.7h, 3h, 3.2h or 3.5h.
In a preferred embodiment of the present invention, in the step (2), the organic silicon source includes tetraethoxysilane.
Preferably, in step (2), the pore-forming agent comprises cetyltrimethylammonium bromide (CTAB) and/or polyvinylpyrrolidone (PVP). After the pore-forming agent is sintered at high temperature, the pore-forming agent is removed, and a shell with a porous structure is formed, so that the permeation of lithium ions is ensured.
Preferably, in the step (2), the solvent includes any one of ethanol, N-methylpyrrolidone or acetone, or a combination of at least two thereof.
Preferably, in the step (2), the alkaline substance comprises ammonia water.
Preferably, in step (2), the core material is milled and sieved prior to mixing with the other reactants.
In a preferred embodiment of the present invention, in step (2), the reaction is carried out for 1.5 to 2.5 hours, for example, 1.5 hours, 1.7 hours, 2 hours, 2.3 hours, 2.5 hours, etc.
Preferably, in step (2), the solid-liquid separation is a filtration separation.
Preferably, in step (2), the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
Preferably, in step (2), the sintering temperature is 450-550 ℃, such as 450 ℃, 475 ℃, 500 ℃, 525 ℃ or 550 ℃.
Preferably, in step (2), the sintering time is 4-6h, such as 4h, 4.5h, 5h, 5.5h or 6h.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) Mixing oxide of metal M with metal lithium, heating to 180-190 ℃ under protective atmosphere, reacting for 20-40min, heating to 195-205 ℃, and reacting for 2.5-3.5h to obtain a core material;
wherein the molar ratio of the metal lithium in the step (1) to the metal M in the oxide of the metal M is 1:1-4;1; the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere; the average particle size of the oxide of the metal M is 200nm-50 mu M;
(2) Mixing the core material, the pore-forming agent cetyl trimethyl ammonium bromide and/or polyvinylpyrrolidone and the organosilicon source tetraethoxysilane in the solvent, adding ammonia water, reacting for 1.5-2.5h, filtering after the reaction, and sintering the obtained solid for 4-6h at 450-550 ℃ in a protective atmosphere to obtain the lithium supplement additive.
In a third aspect, the present invention provides a lithium ion battery comprising the lithium supplement additive according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the lithium supplement additive provided by the invention, the core material has a lithium supplement function, but the conductivity is poor, metal dissolution possibly occurs at a high potential to influence the performance of a battery cell, the conductivity of the material can be improved by virtue of carbon in the shell through coating treatment, the stability of the metal is improved by virtue of SiOx in the shell, and the dissolution is reduced. The lithium supplement additive provided by the invention has high stability and can be completely compatible with the existing lithium battery processing and manufacturing technology.
(2) The preparation method provided by the invention is simple to operate, short in flow and easy for industrial large-scale production.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a lithium supplement additive as follows:
(1) Under the protection of nitrogen, mnO with the average particle size of 5 mu m is adopted 2 Heating the core material and lithium metal at 185 ℃ for 30min (the molar ratio of Li to Mn is 4:1), and heating the core material at 200 ℃ for 3h to obtain the core material.
(2) Grinding the core material in the step (1) and then sieving the ground core material by a 325-mesh sieve; dissolving 10g of CTAB in an organic solvent, then ultrasonically dispersing 1g of the core material in 200g of the solvent, then adding 0.1mL of TEOS, adding 10mL of ammonia water (mass concentration is 25%), reacting for 2h, filtering to obtain a precursor, and sintering the precursor at the high temperature of 500 ℃ for 5h in a nitrogen atmosphere to obtain the lithium supplement additive.
The lithium supplement additive prepared in the embodiment comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 O and a metal Mn, the shell comprising a mixture of SiOx (x = 2) and carbon. The molar ratio of Li to Mn in the inner core is 4:1; the shell is porous structureThe thickness was 8nm.
The test results for the lithium supplement additives prepared in this example are shown in table 1.
Example 2
This example prepares a lithium supplement additive as follows:
(1) Under the protection of nitrogen, fe with the average grain diameter of 20 mu m is adopted 2 O 3 Heating the core material and lithium metal at 183 deg.c for 35min (molar ratio of Li to Fe is 3:1), and heating at 197 deg.c for 3.2 hr to obtain the core material.
(2) Grinding the core material in the step (1) and then sieving the ground core material by a 325-mesh sieve; dissolving 10g of CTAB in an organic solvent, then ultrasonically dispersing 1g of the core material in a 200g solvent, then adding 0.2mL of TEOS, adding 10mL of ammonia water (mass concentration is 25%), reacting for 2.2h, filtering to obtain a precursor, and sintering the precursor at the high temperature of 420 ℃ for 5.5h in a nitrogen atmosphere to obtain the lithium supplement additive.
The lithium supplement additive prepared in the embodiment comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 A mixture of O and a metal Fe, the sheath comprising a mixture of SiOx (x = 2) and carbon. The mol ratio of Li to Fe in the inner core is 3:1; the shell is of a porous structure, and the thickness of the shell is 35nm.
The test results for the lithium supplement additives prepared in this example are shown in table 1.
Example 3
This example prepares a lithium supplement additive as follows:
(1) Under the protection of argon, niO with the average grain diameter of 3 mu m is adopted to be heated with lithium metal for 40min at 180 ℃ (the molar ratio of Li to Ni is 2:1), and then heated for 3.5h at 195 ℃ to obtain the core material.
(2) Grinding the core material in the step (1) and then sieving the ground core material by a 325-mesh sieve; dissolving 5g of PVP in an organic solvent, then ultrasonically dispersing 1g of the core material in a 200g solvent, then adding 0.2mL of TEOS, adding 5mL of ammonia water (mass concentration is 25%), reacting for 1.5h, filtering to obtain a precursor, and sintering the precursor at the high temperature of 450 ℃ for 6h under the argon atmosphere to obtain the lithium supplement additive.
Prepared in this exampleThe lithium supplement additive comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 A mixture of O and metallic Ni, said sheath comprising a mixture of SiOx (x = 2) and carbon. The molar ratio of Li to Ni in the inner core is 2:1; the shell is of a porous structure, and the thickness of the shell is 5nm.
The test results for the lithium supplement additives prepared in this example are shown in table 1.
Example 4
This example prepares a lithium supplement additive as follows:
(1) Under the protection of argon, cuO with the average particle size of 15 mu m is heated with lithium metal for 20min at 190 ℃ (the molar ratio of Li to Cu is 2:1), and then heated for 2.5h at 205 ℃ to obtain the core material.
(2) Grinding the core material in the step (1) and then sieving the ground core material by a 325-mesh sieve; dissolving 5g of PVP in an organic solvent, then ultrasonically dispersing 1g of the core material in a 200-volume solvent, then adding 0.2mL of TEOS, adding 5mL of ammonia water (with the mass concentration of 25%), reacting for 2.5h, filtering to obtain a precursor, and sintering the precursor at the high temperature of 550 ℃ for 4h under the argon atmosphere to obtain the lithium supplement additive.
The lithium supplement additive prepared in the embodiment comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 A mixture of O and a metal Ni, said shell comprising a mixture of SiOx (x = 2) and carbon. The molar ratio of Li to Cu in the inner core is 2:1; the shell is a porous structure, and the thickness of the shell is 15nm.
The test results for the lithium supplement additives prepared in this example are shown in table 1.
Comparative example 1
This comparative example used the core material prepared in example 1 as a control product, and the operation of step (2) of example 1 was not performed thereon.
The results of the product testing of this comparative example are shown in table 1.
Test method
Products provided by each example and comparative example are prepared into lithium ion batteries for testing, and the preparation method comprises the following steps:
(1) manufacturing a positive plate: adding a positive electrode active material Lithium Cobaltate (LCO), a lithium supplement additive, a binder polyvinylidene fluoride (PVDF), a conductive agent Super-P and a mixture of the following components in parts by weight of 92; coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting and welding a tab to obtain a positive electrode piece;
(2) and (3) manufacturing a negative plate: adding artificial graphite, a silicon-carbon composite (or silicon oxide), styrene Butadiene Rubber (SBR) and sodium carboxymethyl cellulose (CMC) serving as negative electrode active materials into deionized water according to the following weight ratio of 91; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding a tab to obtain a negative electrode plate;
(3) preparing a lithium ion battery: assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting electrolyte into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
The electrolyte is 1mol/L LiPF 6 + EC + EMC, the diaphragm is a polyethylene/propylene composite microporous film.
The first capacity and efficiency of the above cell under the conditions of 2.5-4.4V of charging and discharging voltage and 0.1C of charging and discharging rate are shown in Table 1
The battery was charged and discharged at room temperature at a rate of 1C, the voltage was in the range of 2.5 to 4.4V, and the cycle properties obtained by the test are shown in Table 1.
TABLE 1
It can be known from the above examples and comparative examples that the lithium supplement additive provided by each example has high stability and good lithium supplement effect, and can be completely compatible with the existing lithium battery processing and manufacturing technology.
The lithium supplement additive of comparative example 1 was not subjected to silicon carbon composite coating, resulting in a low cycle capacity retention rate.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (27)
1. The lithium supplement additive is characterized by comprising an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Li 2 O and a metal M, the shell comprising SiOx and carbon;
the lithium supplement additive is prepared by adopting the following method, and the method comprises the following steps:
(1) Mixing oxide of metal M with metal lithium, and heating and reacting under protective atmosphere to obtain a core material;
(2) Mixing the core material, the pore-forming agent and the organic silicon source in the step (1) in a solvent, adding an alkaline substance, reacting, carrying out solid-liquid separation after the reaction, and sintering the obtained solid in a protective atmosphere to obtain the lithium supplement additive.
2. The lithium supplement additive according to claim 1, wherein the metal M comprises any one or a combination of at least two of Mn, fe, co, ni, or Cu.
3. The lithium supplement additive according to claim 1, wherein in the lithium supplement additive, li 2 The molar ratio of the lithium element in O to the M element in the metal M is 1:1-4:1.
4. The lithium replenishment additive according to any one of claims 1 to 3, wherein x in the SiOx ranges from 0 to 2 and does not include 0.
5. The lithium supplement additive according to any one of claims 1 to 3, wherein the shell has a thickness of 1 to 50nm.
6. The lithium supplement additive according to any one of claims 1 to 3, wherein the shell has a porous structure.
7. A method for preparing the lithium supplement additive according to any one of claims 1 to 6, wherein the method comprises the following steps:
(1) Mixing oxide of metal M with metal lithium, and heating and reacting under protective atmosphere to obtain a core material;
(2) Mixing the core material, the pore-forming agent and the organic silicon source in the step (1) in a solvent, adding an alkaline substance, reacting, carrying out solid-liquid separation after the reaction, and sintering the obtained solid in a protective atmosphere to obtain the lithium supplement additive.
8. The method according to claim 7, wherein the molar ratio of the metallic lithium in the step (1) to the metal M in the oxide of the metal M is 1:1-4:1.
9. The method of claim 7, wherein the protective atmosphere of step (1) comprises a nitrogen atmosphere and/or an argon atmosphere.
10. The production method according to claim 7, wherein the average particle diameter of the metal M oxide in the step (1) is 200nm to 50 μ M.
11. The method according to claim 7, wherein the heating reaction in the step (1) is a two-stage heating.
12. The method of claim 11, wherein the first of the two stages of heating is at a temperature of 180-190 ℃.
13. The method according to claim 11, wherein the first heating period of the two heating stages is 20-40min.
14. The method according to claim 11, wherein the temperature of the second heating in the two heating stages is 195 to 205 ℃.
15. The method according to claim 11, wherein in the two-stage heating, the second stage heating is carried out for 2.5 to 3.5 hours.
16. The method according to claim 7, wherein in the step (2), the organic silicon source comprises tetraethoxysilane.
17. The method according to claim 7, wherein in the step (2), the pore-forming agent comprises cetyltrimethylammonium bromide and/or polyvinylpyrrolidone.
18. The method according to claim 7, wherein in the step (2), the solvent comprises any one of ethanol, N-methylpyrrolidone or acetone, or a combination of at least two thereof.
19. The method according to claim 7, wherein in the step (2), the basic substance includes ammonia water.
20. The method of claim 7, wherein in step (2), the core material is ground and sieved before being mixed with the other reactants.
21. The method according to claim 7, wherein in the step (2), the reaction is carried out for 1.5 to 2.5 hours.
22. The production method according to claim 7, wherein in the step (2), the solid-liquid separation is a filtration separation.
23. The method according to claim 7, wherein in the step (2), the protective atmosphere includes a nitrogen atmosphere and/or an argon atmosphere.
24. The production method according to claim 7, wherein in the step (2), the temperature of the sintering is 450 to 550 ℃.
25. The method according to claim 7, wherein in the step (2), the sintering time is 4-6h.
26. The method for preparing according to claim 7, characterized in that it comprises the following steps:
(1) Mixing oxide of metal M with metal lithium, heating to 180-190 ℃ under protective atmosphere, reacting for 20-40min, heating to 195-205 ℃, and reacting for 2.5-3.5h to obtain a core material;
wherein the molar ratio of the metal lithium in the step (1) to the metal M in the oxide of the metal M is 1:1-4:1; the protective atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere; the average particle size of the oxide of the metal M is 200nm-50 mu M;
(2) Mixing the core material, the pore-forming agent cetyl trimethyl ammonium bromide and/or polyvinylpyrrolidone and the organosilicon source tetraethoxysilane in the solvent, adding ammonia water, reacting for 1.5-2.5h, filtering after the reaction, and sintering the obtained solid for 4-6h at 450-550 ℃ in a protective atmosphere to obtain the lithium supplement additive.
27. A lithium ion battery comprising the lithium supplement additive according to any one of claims 1 to 6.
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| CN111640932B (en) * | 2020-06-03 | 2022-05-13 | 无锡零一未来新材料技术研究院有限公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| CN112054204B (en) * | 2020-09-16 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Lithium supplement reagent and preparation method and application thereof |
| CN112290022B (en) * | 2020-10-20 | 2022-07-05 | 合肥国轩高科动力能源有限公司 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
| CN113020589A (en) * | 2021-02-26 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Stable metal lithium powder and preparation method and application thereof |
| CN113036106A (en) * | 2021-03-09 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Composite lithium supplement additive and preparation method and application thereof |
| CN114097113A (en) * | 2021-03-26 | 2022-02-25 | 宁德新能源科技有限公司 | Positive electrode lithium supplement material, positive electrode plate containing material and electrochemical device |
| CN115148962A (en) * | 2021-06-15 | 2022-10-04 | 中南大学 | N-C @ Li 5 FeO 4 Composite lithium supplement additive, preparation thereof and application thereof in lithium ion battery |
| CN113800575B (en) * | 2021-08-17 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recycling lithium battery positive electrode material |
| CN116002764B (en) * | 2021-10-27 | 2023-12-29 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing additive, preparation method and application thereof |
| CN115312769A (en) * | 2021-12-30 | 2022-11-08 | 深圳市德方创域新能源科技有限公司 | Lithium supplement additive and particle size control method and application thereof |
| CN115312712A (en) * | 2022-05-31 | 2022-11-08 | 深圳市德方创域新能源科技有限公司 | Lithium supplement additive, preparation method thereof and secondary battery |
| CN115458742A (en) * | 2022-10-19 | 2022-12-09 | 赣州立探新能源科技有限公司 | A kind of hard carbon material and preparation method thereof |
| CN115566288A (en) * | 2022-10-21 | 2023-01-03 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplement additive and preparation method and application thereof |
| CN119627115A (en) * | 2023-09-12 | 2025-03-14 | 江阴纳力新材料科技有限公司 | Carbon-coated current collector, preparation method of lithium-supplementing-containing coating material and carbon-coated current collector |
| CN117638081B (en) * | 2024-01-23 | 2024-04-26 | 上海瑞浦青创新能源有限公司 | Composite lithium supplement and preparation method thereof, positive electrode sheet, and lithium ion battery |
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